Herbicidal derivatives of pyrid-2-yloxyphenoxy-acetic acids and esters

ABSTRACT

New phenoxy-alkanecarboxylic acid derivatives which have a herbicidal action and which are effective in regulating plant growth are described. They correspond to the formula ##STR1## in which A is the cyano group, a carboxylic acid, a salt, ester, thioester or amide thereof, 
     Q is a mono- to trisubstituted phenyl or pyrid-2-yl radical, 
     R 3  is hydrogen, halogen, cyano, nitro, alkyl or carbamoyl, 
     R 4  is alkyl, alkoxyalkyl, cycloalkyl, alkenyl, alkynyl, phenyl or benzyl, and 
     X, Y and Z are each oxygen or sulfur. 
     They can be used as selective herbicides in cereal and rice crops, or for reducing the vegetative growth, for example in soya-bean crops, and also for defoliation and desiccation in cotton or potato crops shortly before the harvesting thereof.

This is a divisional of application Ser. No. 019,999 filed on Mar. 12,1979 now U.S. Pat. No. 4,233,054.

The present invention relates to new, herbicidally effectivephenoxy-alkanecarboxylic acid derivatives, to processes for producingthem, also to herbicidal compositions which contain these new compoundsas active substances, and also to processes for the selective control ofweeds in crops of cultivated plants by use of the new active substancesor of compositions which contain them.

The new active substances correspond to the formula I ##STR2## in whichQ is a radical ##STR3## A is the cyano group or a radical --COB, B is aradical --OR₅, --SR₆ or --NR₇ R₈,

R₁ is a halogen atom,

n is the number 0, 1 or 2,

R₂ is a halogen atom or the trifluoromethyl, nitro, cyano, carbamoyl orthiocarbamoyl group,

R₃ is hydrogen, halogen, a C₁ -C₄ -alkyl group, or the nitro, cyano orcarbamoyl group,

R₄ is C₁ -C₆ -alkyl, C₂ -C₆ -alkenyl, C₂ -C₆ -alkynyl, benzyl or phenylboth optionally substituted by halogen, or it is C₂ -C₆ -alkoxyalkyl orC₃ -C₁₂ -cycloalkyl,

R₅ is hydrogen or the cation of a base ##STR4## wherein M is an alkalimetal cation or alkaline-earth metal cation or an Fe, Cu, Zn, Mn or Nication, or an ammonium group ##STR5## and m as integer 1, 2 or 3 takesaccount of the valency of the cation, whilst R_(a), R_(b), R_(c) andR_(d) independently of one another are each hydrogen, benzyl or a C₁ -C₄-alkyl group which is unsubstituted or substituted by --OH, --NH₂ or C₁-C₄ -alkoxy,

R₅ and R₆ are each a C₁ -C₁₈ -alkyl group which is unsubstituted or issubstituted by halogen, nitro, cyano, C₁ -C₈ -alkoxy, C₂ -C₈-alkoxyalkoxy, or by C₃ -C₆ --alkenyloxy, C₁ -C₈ -alkylthio, C₂ -C₈-alkanoyl, C₂ -C₈ --acyloxy, C₂ -C₈ -alkoxycarbonyl, carbamoyl, or bybis-(C₁ -C₄ -alkyl)-amino, tris-(C₁ -C₄ -alkyl)-ammonium, C₃ -C₈-cycloalkyl or C₃ -C₈ -cycloalkenyl, optionally also by a phenoxy groupor a 5-6-membered heterocyclic radical having 1 to 3 hetero atoms, eachof which is unsubstituted or in its turn mono- or polysubstituted byhalogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; or R₅ and R₆ are each a C₃-C₁₈ -alkenyl group which is unsubstituted or is mono- totetrasubstituted by halogen or monosubstituted by phenyl ormethoxycarbonyl; or they are each a C₃ -C₈ -alkynyl group; or a C₃ -C₁₂-cycloalkyl group which is unsubstituted or substituted by halogen or C₁-C₄ -alkyl; or they are each a C₃ -C₈ -cycloalkenyl group; or a phenylgroup which is unsubstituted or is mono- or polysubstituted by halogen,C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, NO₂, CF₃, COOH, CN,OH, SO₃ H, NH₂ or --NH(C₁ -C₄ -alkyl) or --N(C₁ -C₄ -alkyl)₂ ; or R₅ andR₆ are each a 5- to 6-membered heterocyclic ring having 1 to 3 heteroatoms, and

R₇ and R₈ are each hydrogen, or an unsubstituted or substituted(cyclo)aliphatic or aromatic radical, or

R₇ and R₈ together with the nitrogen atom to which they are attached canalso form a heterocyclic ring, and

X, Y and Z are each an oxygen atom or sulfur atom.

The alkyl groups in this formula can be either branched-chain orstraight-chain, and they contain the given number of carbon atoms.

The radicals R₇ and R₈ can be hydrogen or aliphatic, cycloaliphatic oraromatic radicals, or, together with the nitrogen atom to which they areattached, they can form a preferably 5-6-membered heterocycle, which canalso contain a second hetero atom. Preferred however are hydrogen, loweralkyl groups and also branched-chain alkenyl and alkynyl groups, such asallyl, methallyl, 2,2-dimethylallyl, 2,2-dimethylpropargyl and2,2-diethylpropargyl.

The new active substances of the formula I according to the presentinvention have a herbicidal action on pre- and post-emergenceapplication, and can be used as a herbicide in crops of both mono- anddicotyledonous plants. To be mentioned in particular is their actionagainst the weed brome grass (bromus tectorum).

Furthermore, they have favourable growth-regulating effects (growthinhibition). They inhibit especially the growth of dicotyledonousplants. Examples of the profitable application of the compoundsaccording to the invention are:

reduction of vegetative growth in the case of soya-bean plants andsimilar leguminosae, an effect which leads to an increase in the yieldof these crops;

reduction of the undesirable growth of side shoots on tobacco plants,the leading shoots of which have been cut, an effect which promotes theformation of larger and better leaves;

reduction of the growth of grass and of dicotyledonous plants, such asfruit trees, ornamental trees, shrubs and hedges, for the purpose ofeconomising in the amount of cutting work; and

desiccation and defoliation of plants, for example potato plants andcotton, shortly before harvesting.

The compounds of the present invention are negligibly toxic towarm-blooded animals, and application of these compounds presents noproblems. The amount applied is between 0.1 and 5 kg per hectare.

The new compounds of the formula I are produced by methods known per se,for example by synthesis means.

An appropriately substituted phenol or thiophenol of the formula II##STR6## in which R₁, n, R₂, R₃, X and Y have the meanings given underthe formula I, is reacted in an inert solvent or diluent, in thepresence of a base as acid-binding agent, with a derivative, substitutedin the 2-position by ZR₄, of a 2-haloacetic acid of the formula III##STR7## in which A, R₄ and Z have the meanings given under the formulaI, and "Hal" is a halogen atom, preferably chlorine or bromine.

The compounds of the formula I are also obtained by reacting anappropriately substituted derivative of a 2-haloacetic acidcorresponding to the formula IV ##STR8## in which A, Q, R₃, X and Y havethe meanings given under the formula I, and "Hal" is a halogen atom,preferably chlorine or bromine, in an inert solvent or diluent, in thepresence of a base as acid-binding agent, with an alcohol or thiol ofthe formula V

    H--Z--R.sub.4                                              (V)

in which R₄ and Z have the meanings given under the formula I.

The reactions mentioned can be performed in the presence or absence ofsolvents or diluents inert to the reactants. Polar organic solvents suchas methyl ethyl ketone, dimethylformamide, dimethylsulfoxide, and soforth, are preferred. The reaction temperatures are between 0° and 200°C., and the duration of the reaction, depending on starting material,the chosen reaction temperature and the solvent, is between 1 hour andseveral days. The reaction is performed as a rule at normal pressure.The customary bases (condensation agents), for example KOH, NaOCH₃,NaHCO₃, K₂ CO₃, potassium-tert-butylate, and so forth, are suitable forthe reaction, but also organic bases are suitable, such astriethylamine, and the like.

The compounds of the formula I are new. Structurally similar2-phenoxy-2-alkoxy-acetic acid amides having a herbicidal action havebeen described in the U.S. Pat. Nos. 4,049,423, 4,049,424 and 4,050,923.

Some of the starting materials of the formulae II to V are known.Starting materials of these formulae not yet described can be readilyproduced by customary processes and techniques. Phenoxyphenols of theformula II can be produced for example according to the methodsdescribed in J.Am.Chem.Soc. 61, 2702 (1939) or in Chem. Abstract 52,9006b (1958).

The production of phenoxy-alkanecarboxylic acid esters of the formula Iis illustrated in the Examples which follow. Further active substancesproduced in a corresponding manner are listed in the Tables subsequentlygiven. Temperature values are in degrees Centigrade, and `parts` and`percentages` relate to the weight.

EXAMPLE 1 2-[4-(4'-Trifluoromethylphenoxy)-phenoxy]-2-methoxyacetic acidmethyl ester ##STR9##

To a solution of 33.3 g (0.3 mol) of potassium tertbutylate in 300 ml oftert-butanol is firstly added 76.2 g (0.3 mol) of4-(4'-trifluoromethylphenoxy)-phenol, and then 54.9 g (0.3 mol) of2-bromo-2-methoxyacetic acid methyl ester is added dropwise. After beingstirred for 3 hours at 35°, the reaction mixture is poured into 1200 mlof water, and then extracted twice with 300 ml of chloroform each time.The combined extracts are washed three times with 300 ml of saturatedaqueous NaCl solution each time, dried over magnesium sulfate andconcentrated by evaporation. The solvent is distilled off to leavebehind 97.3 g (0.274 mol) of the title product in the form of oil whichhas a refractive index of n_(D) ²² =1.5119, and which was identified bymeans of the NMR spectrum.

EXAMPLE 22-Methoxy-2-[3-(3',5'-dichloropyridyl-2'-oxy)-6-chlorophenoxy]-aceticacid methyl ester ##STR10##

14.5 g (0.05 mol) of 3-(3',5'-dichloropyridyl-2'-oxy)-6-chlorophenol isadded to a solution of 6.2 g (0.055 mol) of potassium tert-butylate in140 ml of tert-butanol, and at 40° 10 g (0.055 mol) of2-bromo-2-methoxy-acetic acid methyl ester is added dropwise. Thereaction mixture is stirred at 25° for 6 hours. The potassium bromide isthen filtered off and the filtrate is concentrated by evaporation. Theoil which remains is taken up in ether and extracted with water. Theether phase is dried with magnesium sulfate and concentrated byevaporation. The yield after drying under high vacuum is 14 g (71% oftheory) of the title compound having the refractive index n_(D) ³⁰=1.5675.

                                      TABLE 1                                     __________________________________________________________________________           6                                                                       ##STR11##                                                                     No.                                                                              ##STR12##                                                                            X                                                                               ##STR13##                                                                           Y                                                                               ZR.sub.4                                                                          A             constants Physical                     __________________________________________________________________________    1  4'CF.sub.3                                                                           O H     O OCH.sub.3                                                                         COOCH.sub.3   n.sub.D.sup.22 1.5199                   2  4'CF.sub.3                                                                           O H     O OCH.sub.3                                                                         COOH                                                  3  4'CF.sub.3                                                                           O H     O OCH.sub.3                                                                         COOC.sub.2 H.sub.5                                    4  4'CF.sub.3                                                                           O H     O OCH.sub.3                                                                         COO.sub.n C.sub.3 H.sub.7                             5  4'CF.sub.3                                                                           O H     O OCH.sub.3                                                                         COOiC.sub.3 H.sub.7                                   6  4'CF.sub.3                                                                           O H     O OCH.sub.3                                                                         COO.sub.s C.sub.4 H.sub.9                             7  4'CF.sub.3                                                                           O H     O OCH.sub.3                                                                         COOiC.sub.4 H.sub.9                                   8  4'CF.sub.3                                                                           O H     O OCH.sub.3                                                                          ##STR14##                                            9  4'CF.sub.3                                                                           O H     O OCH.sub.3                                                                          ##STR15##                                            10 4'CF.sub.3                                                                           O H     O OCH.sub.3                                                                          ##STR16##                                            11 4'CF.sub.3                                                                           O H     O OCH.sub.3                                                                         COOCH.sub.2CHCH.sub.2                                 12 4'CF.sub.3                                                                           O H     O OCH.sub.3                                                                         COSH                                                  13 4'CF.sub.3                                                                           O H     O OCH.sub.3                                                                         COSCH.sub.3                                           14 4'CF.sub.3                                                                           O H     O OCH.sub.3                                                                         COSCH.sub.2CHCH.sub.2                                 15 4'CF.sub.3                                                                           O H     O OCH.sub.3                                                                          ##STR17##                                            16 4'CF.sub. 3                                                                          O H     O OCH.sub.3                                                                          ##STR18##                                            17 4'CF.sub.3                                                                           O H     O OCH.sub.3                                                                         CONHC(CH.sub.3).sub.2 CCH                             18 4'CF.sub.3                                                                           O H     O OCH.sub.3                                                                         CONHC(C.sub.2 H.sub.5).sub.2 CCH                      19 4'CF.sub.3                                                                           O H     O OCH.sub.3                                                                         COOC.sub.2 H.sub.4 OCH.sub.3                          20 4'CF.sub.3                                                                           O H     O OCH.sub.3                                                                         CN                                                    21 4'CF.sub.3                                                                           O H     O OC.sub.2 H.sub.5                                                                  COOCH.sub.3                                           22 2'Cl, 4'CF.sub.3                                                                     O H     O OCH.sub.3                                                                         COOCH.sub.3   n.sub.D.sup.20 1.5206                   23 2'Cl, 4'CF.sub.3                                                                     O H     O OCH.sub.3                                                                         COOH                                                  24 2'Cl, 4'CF.sub.3                                                                     O H     O OCH.sub.3                                                                         COOC.sub.2 H.sub.5                                    25 2'Cl, 4'CF.sub.3                                                                     O H     O OCH.sub.3                                                                         COO.sub.n C.sub.3 H.sub.7                             26 2'Cl, 4'CF.sub.3                                                                     O H     O OCH.sub.3                                                                         COOiC.sub.3 H.sub.7                                   27 2'Cl, 4'CF.sub.3                                                                     O H     O OCH.sub. 3                                                                        COOC.sub.4 H.sub.9                                    28 2'Cl, 4'CF.sub.3                                                                     O H     O OCH.sub.3                                                                         COOiC.sub.4 H.sub.9                                   29 2'Cl, 4'CF.sub.3                                                                     O H     O OCH.sub.3                                                                          ##STR19##                                            30 2'Cl, 4'CF.sub.3                                                                     O H     O OCH.sub.3                                                                          ##STR20##                                            31 2'Cl, 4'CF.sub.3                                                                     O H     O OCH.sub.3                                                                          ##STR21##                                            32 2'Cl, 4'CF.sub.3                                                                     O H     O OCH.sub.3                                                                         COOC.sub.2 H.sub.4 OCH.sub.3                          33 2'Cl, 4'CF.sub.3                                                                     O H     O OCH.sub.3                                                                         COOCH.sub.2CHCH.sub.2                                 34 2'Cl, 4'CF.sub.3                                                                     O H     O OCH.sub.3                                                                         COOCH.sub.2CHCN                                       35 2'Cl, 4'CF.sub.3                                                                     O H     O OCH.sub.3                                                                         COSCH.sub.3                                           36 2'Cl, 4'CF.sub.3                                                                     O H     O OCH.sub.3                                                                         COSC.sub.2 H.sub.5                                    37 2'Cl, 4'CF.sub.3                                                                     O H     O OCH.sub.3                                                                         COSCH.sub.2CHCH.sub.2                                 38 2'Cl, 4'CF.sub.3                                                                     O H     O OCH.sub.3                                                                          ##STR22##                                            39 2'Cl, 4'CF.sub.3                                                                     O H     O OCH.sub.3                                                                          ##STR23##                                            40 2'Cl, 4'CF.sub.3                                                                     O H     O OCH.sub.3                                                                         CONHC(CH.sub.3).sub.2 CCH                             41 2'Cl, 4'CF.sub.3                                                                     O H     O OCH.sub.3                                                                         CONHC(C.sub.2 H.sub.5).sub.2 CCH                      42 2'Cl, 4'CF.sub.3                                                                     O H     O OCH.sub.3                                                                         CN                                                    43 2'Cl, 4'CF.sub.3                                                                     O H     O OC.sub.2 H.sub.5                                                                  COOCH.sub.3                                           44 2'Cl, 4'CF.sub.3                                                                     O H     O OCH.sub.3                                                                         CON(CH.sub.3).sub.2                                   45 2'Cl, 4'CF.sub.3                                                                     O H     O OCH.sub.3                                                                         COOCH.sub.3                                           46 2'NO.sub.2 4'Cl                                                                      O H     O OCH.sub.3                                                                         COOCH.sub.3   m.p. 62-65°                      47 2'CN, 4'Cl                                                                           O H     O OCH.sub.3                                                                         COOCH.sub.3   n.sub.D.sup.20 1.5496                   48 2'CSNH.sub.2,4'Cl                                                                    O H     O OCH.sub.3                                                                         COOCH.sub.3                                           49 4'Cl   O H     O OCH.sub.3                                                                         COOCH.sub.3   n.sub.D.sup.20 1.5550                   50 2'Cl, 4'Cl                                                                           O H     O OCH.sub.3                                                                         COOCH.sub.3   n.sub.D.sup.20 1.5641                   __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________     ##STR24##                                                                    __________________________________________________________________________     No.                                                                              ##STR25##                                                                           X                                                                               ##STR26##                                                                            Y                                                                               ZR.sub.4                                                                               A             constants Physical                __________________________________________________________________________    1  2'Cl, 4'Cl                                                                          O 6 NO.sub.2                                                                           O OCH.sub.3                                                                              COOCH.sub.3                                      2  2'Cl, 4'Cl                                                                          O 6 CN   O OCH.sub.3                                                                              COOCH.sub.3                                      3  2'Cl, 4'Cl                                                                          O 6 Cl   O OCH.sub.3                                                                              COOCH.sub.3   n.sub.D.sup.20 1.5659              4  2'NO.sub.2,4'Cl                                                                     O 6 Cl   O OCH.sub.3                                                                              COOCH.sub.3   n.sub.D.sup.20 1.5598              5  2'NO.sub.2,4' Cl                                                                    O H      O OCH.sub.3                                                                              COOCH.sub.3                                      6  2'Cl, 4'Br                                                                          O 6 Cl   O OCH.sub.3                                                                              COOCH.sub.3   n.sub.D.sup.20 1.5710              7  2'CN, 4'Cl                                                                          O H      O OCH.sub.3                                                                              COOCH.sub.3   n.sub.D.sup.20 1.5645              8  2'CN, 4'Cl                                                                          O 6 NO.sub.2                                                                           O OCH.sub.3                                                                              COOCH.sub.3   n.sub.D.sup.20 1.5598              9  2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O OCH.sub.3                                                                              COOCH.sub.3   n.sub.D.sup.20 1.5320              10 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           O OCH.sub.3                                                                              COOCH.sub.3   n.sub.D.sup.23 1.5268              11 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O SCH.sub.3                                                                              COOCH.sub.3   n.sub.D.sup.20 1.5433              12 2'Br, 4'Cl                                                                          O 6 Cl   O OCH.sub.3                                                                              COOCH.sub.3   n.sub.D.sup.20 1.5707              13 2'Cl, 4CF.sub.3                                                                     O 6 Cl   O SC.sub.2 H.sub.5                                                                       COOCH.sub.3   n.sub. D.sup.20 1.5402             14 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O OCH.sub.3                                                                              COOC.sub.2 H.sub.5                                                                          n.sub.D.sup.20 1.5172              15 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O OCH.sub.3                                                                              COOH          n.sub.D.sup.20                     __________________________________________________________________________                                               1.5348                              No.                                                                              ##STR27##                                                                           X                                                                               ##STR28##                                                                            Y                                                                               ZR.sub.4                                                                               A             Constants Physical                __________________________________________________________________________    16 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           O OCH.sub.3                                                                              COOH          n.sub.D.sup.20 1.5402              17 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           O OCH.sub.3                                                                              COOC.sub.2 H.sub.5                                                                          n.sub.D.sup.20 1.5314              18 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O OCH.sub.3                                                                              COO.sub.t C.sub.4 H.sub.9                                                                   n.sub.D.sup.20 1.5252              19 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           O SCH.sub.3                                                                              COOCH.sub.3   n.sub.D.sup.20 1.5510              20 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           O SC.sub.2 H.sub.5                                                                       COOCH.sub.3   n.sub.D.sup.20 1.5427              21 2'CN, 4'Cl                                                                          O 6 NO.sub.2                                                                           O OCH.sub.3                                                                              COOCH.sub.3                                      22 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O OCH.sub.3                                                                              COOC.sub.2 H.sub.4 OCH.sub.3                     23 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O SCH.sub.3                                                                              COOCH.sub.2 CHCH.sub.2                           24 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           O SCH.sub.3                                                                               ##STR29##                                       25 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           O SCH.sub.3                                                                               ##STR30##                                       26 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O SCH.sub.3                                                                              COOC.sub.2 H.sub.4 SCH.sub.3                     27 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O SCH.sub.3                                                                              COSCH.sub.2 CHCH.sub.2                           28 2'Cl, 4CF.sub.3                                                                     O 6 NO.sub.2                                                                           O OCH.sub.3                                                                               ##STR31##                                       29 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           O OCH.sub.3                                                                               ##STR32##                                       30 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           O OCH.sub.3                                                                              COC.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.2                                   H.sub.5                                          31 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O OCH.sub.3                                                                              COOC.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.2                                  H.sub.5                                          32 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O OCH.sub.3                                                                              COOC.sub.2 H.sub.4 Cl                            33 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           O OCH.sub.3                                                                              COOC.sub.2 H.sub.4 Cl                            34 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O SCH.sub.3                                                                              COOC.sub.2 H.sub.4 Cl                            35 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           O OCH.sub.3                                                                              COOC.sub.2 H.sub.4 CN                            36 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O OCH.sub.3                                                                              COOC.sub.2 H.sub.4 CN                            37 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O OCH.sub.3                                                                              COOCH.sub.2 CF.sub.3                             38 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           O OCH.sub.3                                                                              COOCH.sub.2 CF.sub.3                             39 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O                                                                                ##STR33##                                                                             COOCH.sub.3   n.sub.D.sup.21 1.5459              40 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O                                                                                ##STR34##                                                                             COOCH.sub.3   m.p. 122°                   41 2'Cl, 4'Cl                                                                          O 6 Cl   O                                                                                ##STR35##                                                                             COOCH.sub.3   m.p. 102°                   42 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O                                                                                ##STR36##                                                                             COOCH.sub.3   m.p. 95°                    43 2'Cl, 4'Cl                                                                          O 6 Cl   O                                                                                ##STR37##                                                                             COOCH.sub.3   m.p. 85°                    44 2'Cl, 4'Cl                                                                          O 6 Cl   O                                                                                ##STR38##                                                                             COOCH.sub.3                                      45 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           S OCH.sub.3                                                                              COOCH.sub.3                                      46 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           S SCH.sub.2                                                                              COOCH.sub.3                                      47 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           S SC.sub.2 H.sub.5                                                                       COOC.sub.2 H.sub.5                               48 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           S SC.sub.2 H.sub.5                                                                       COOCH.sub.3                                      49 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           O O.sub.s C.sub.4 H.sub.9                                                                COOCH.sub.3   n.sub.D.sup.21 1.5188              50 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O OC.sub.2 H.sub.5                                                                       COOC.sub.2 H.sub.5                                                                          n.sub.D.sup.21 1.5145              51 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O O.sub.n C.sub.3 H.sub.7                                                                CO.sub.n C.sub.3 H.sub.7                                                                    n.sub.D.sup.21 1.5090              52 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O O.sub.s C.sub.4 H.sub.9                                                                COO.sub.s C.sub.4 H.sub.9                                                                   n.sub.D.sup.21 1.5069              53 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O O.sub.s C.sub.4 H.sub.9                                                                COOCH.sub.3   n.sub.D.sup.21 1.5060              54 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           O OC.sub.2 H.sub.5                                                                       COOCH.sub.3   n.sub.D.sup.22 1.5261              55 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           O O.sub.s C.sub.4 H.sub.9                                                                COO.sub.s C.sub.4 H.sub.9                                                                   n.sub.D.sup.21 1.5179              56 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           O O.sub.n C.sub.3 H.sub.7                                                                COO.sub.n C.sub.3 H.sub.7                                                                   n.sub.D.sup.21 1.5202              57 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           O OCH.sub.3                                                                               ##STR39##                                       58 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           O OCH.sub.3                                                                              COOCH.sub.2CH                                    59 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           O OCH.sub.3                                                                               ##STR40##                                       60 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           O OCH.sub.3                                                                              CON(CH.sub.3).sub.2                              61 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O SCH.sub.3                                                                              COOCH.sub.3                                      62 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O SC.sub.2 H.sub.5                                                                       COOCH.sub.3                                      63 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O OCH.sub.3                                                                              CONHC(CH.sub.2)CCH                               64 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           O OCH.sub.3                                                                              CON(CH.sub.3)OCH.sub.3                           65 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           O OCH.sub.3                                                                              CON(C.sub.2 H.sub.5).sub.2 C CH                  66 2'Cl, 4'Cl                                                                          O 6 Cl   O OCH.sub.3                                                                              CON(CH.sub.3).sub.2                              67 2'Cl, 4'CF.sub.3                                                                    O 6 NO.sub.2                                                                           O SCH.sub.3                                                                              COOCH.sub.2 CHCH.sub.2                           68 2'Cl, 4'CF.sub.3                                                                    O 6 Cl   O OCH.sub.2 CHCH.sub.2                                                                   COOCH.sub.3                                      __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________     ##STR41##                                                                     No                                                                               ##STR42##  X                                                                               ##STR43##                                                                           Y                                                                               ZR.sub.4                                                                          A            constants Physical                  __________________________________________________________________________    1  3'Cl, 5'Cl O H     O OCH.sub.3                                                                         COOCH.sub.3  n.sub.D.sup.30 1.5633                2  3'Cl, 5'Cl O H     O OCH.sub.3                                                                         COOC.sub.2 H.sub.5                                3  3'Cl, 5'Cl O H     O OCH.sub.3                                                                         COOH                                              4  3'Cl, 5'Cl O H     O OCH.sub.3                                                                         CN                                                5  3'Cl, 5'Cl O H     O SCH.sub.3                                                                         COOCH.sub.3                                       6  3'Br, 5'Br O H     O OCH.sub.3                                                                         COOCH.sub.3                                       7  3'Br, 5'Cl O H     O OCH.sub.3                                                                         COOCH.sub.3                                       8  3'CN, 5'Cl O H     O OCH.sub.3                                                                         COOCH.sub.3                                       9  3'Cl, 5'CN O H     O OCH.sub.3                                                                         COOCH.sub.3                                       10 3'Cl, 5'Br O H     O OCH.sub.3                                                                         COOCH.sub.3                                       11 3'Br, 5'Br O H     O OCH.sub.3                                                                         COOC.sub.2 H.sub.5                                12 3'Cl, 5'Cl O H     O OCH.sub.3                                                                         COOCH.sub.2CHCH.sub.2                             13 3'Cl, 5'Cl O H     O OCH.sub.3                                                                         CON(CH.sub.3).sub.2                               14 3'Cl, 5'Cl O H     O SCH.sub.3                                                                          ##STR44##                                        __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________     ##STR45##                                                                     No.                                                                              ##STR46##  X                                                                               ##STR47##                                                                           Y                                                                               ZR.sub.4                                                                          A           constants Physical                   __________________________________________________________________________    1  3'Cl 5'Cl  O 6 Cl  O OCH.sub.3                                                                         COOCH.sub.3 n.sub.D.sup.30 1.5675                 2  3'Cl 5'Cl  O 6 Cl  O OCH.sub.3                                                                         COOH                                              3  3'Cl 5'Cl  O 6 Cl  O OCH.sub.3                                                                         COOC.sub.2 H.sub.5                                4  3'Cl 5'Cl  O 6 Cl  O OCH.sub.3                                                                         COO.sub.n C.sub.3 H.sub.7                         5  3'Cl 5'Cl  O 6 Cl  O OCH.sub.3                                                                         COOiC.sub.3 H.sub.7                               6  3'Cl 5'Cl  O 6 Cl  O OCH.sub.3                                                                          ##STR48##                                        7  3'Cl 5'Cl  O 6 Cl  O OCH.sub.3                                                                          ##STR49##                                        8  3'Cl 5'Cl  O 6 Cl  O OCH.sub.3                                                                          ##STR50##                                        9  3'Cl 5'Cl  O 6 Cl  O OCH.sub.3                                                                         COOCH.sub.2 CHCH.sub.2                            10 3'Cl 5'Cl  O 6 Cl  O OCH.sub.3                                                                         COS.sub.i C.sub.3 H.sub.7                         11 3'Cl 5'Cl  O 6 Cl  O OCH.sub.3                                                                         COSCH.sub.3                                       12 3'Cl 5'Cl  O 6 Cl  O OCH.sub.3                                                                         COSCH.sub.2 CHCH.sub.2                            13 3'Cl 5'Cl  O 6 Cl  O OCH.sub.3                                                                          ##STR51##                                        14 3'Cl 5'Cl  O 6 Cl  O OCH.sub.3                                                                          ##STR52##                                        15 3'Cl 5'Cl  O 6 Cl  O OCH.sub.3                                                                         CN                                                16 3' Cl 5'Cl O 6 Cl  O OCH.sub.3                                                                         CONHC(CH.sub.3).sub.2 CCH                         17 3'Cl 5'Cl  O 6 Cl  O OCH.sub.3                                                                         CONHC(C.sub.2 H.sub.5).sub.2 CCH                  18 3'Cl, 5'Cl O 6 Br  O OCH.sub.3                                                                         COOCH.sub.3 n.sub.D.sup.20 1.5815                 19 3'Cl, 5'Cl O 6 NO.sub.2                                                                          O OCH.sub.3                                                                         COOCH.sub.3 n.sub.D.sup.20 1.5830                 20 3'Cl, 5'Cl O 6 Br  O OCH.sub.3                                                                         CON(CH.sub.3).sub.2                               21 3'Br, 5'Br O 6 Br  O OCH.sub.3                                                                         COOCH.sub.3                                       22 3'Cl, 5'Cl O 6 Cl  O SCH.sub.3                                                                         COOCH.sub.3                                       23 3'Cl, 5'Cl O 6 Br  O SCH.sub.3                                                                         COOCH.sub.3                                       24 3'Cl, 5'Cl O 6 NO.sub.2                                                                          O SCH.sub.3                                                                         COOCH.sub.3                                       25 3'CN, 5'Cl O 6 Cl  O SCH.sub.3                                                                         COOCH.sub.3                                       26 3'Cl 5'Br  O 6 Cl  O OCH.sub.3                                                                         COOCH.sub.3                                       27 H 5'Cl     O 6 Cl  O OCH.sub.3                                                                         COOCH.sub.3                                       __________________________________________________________________________

The new active substances of the formula I are stable compounds whichare soluble in customary organic solvents, such as alcohols, ethers,ketones, dimethylformamide, dimethyl sulfoxide, and so forth.

The compositions according to the invention are produced in a mannerknown per se by the intimate mixing and grinding of the activesubstances of the formula I with suitable carriers and/or distributingagents, optionally with the addition of antifoaming agents, wettingagents, dispersing agents and/or solvents, all inert to the activesubstances. The active substances can be obtained and used in thefollowing forms:

solid preparations: dusts, scattering agents, granules, (coatedgranules, impregnated granules and nomogeneous granules);

water-dispersible concentrates of active substance: wettable powders,pastes, emulsions and emulsion concentrates; and

liquid preparations: solutions.

The concentration of active substance in the compositions according tothe invention is 1 to 80 percent by weight, and when being applied thecompositions can if necessary contain the active substances also at alower concentration, such as about 0.05 to 1 percent by weight.

Other biocidal active substances can be mixed with describedcompositions according to the invention.

In the following are given some examples of preparations or compositionsof the types mentioned above.

Granulate

The following substances are used to produce a 5% granulate:

5 parts of one of the active substances of the formula I,

0.25 part of epichlorohydrin,

0.25 part of cetyl polyglycol ether,

3.50 parts of polyethylene glycol, and

91 parts of kaolin (particle size: 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin, and dissolved in 6parts of acetone; polyethylene glycol and cetyl polyglycol ether arethen added. The solution thus obtained is sprayed onto kaolin, and theacetone is subsequently evaporated off in vacuo.

Wettable powder

The following constituents are used to produce (a) a 70% wettable powderand (b) a 10% wettable powder:

(a)

70 parts of 2-[4-(4'-trifluoromethyl-phenoxy)-phenoxy]-2methoxy-aceticacid methyl ester,

5 parts of sodium dibutyl-naphthalene sulfonate,

3 parts of naphthalenesulfonic acid/phenolsulfonic acid/formaldehydecondensate (3:2:1),

10 parts of kaolin, and

12 parts of Champagne chalk;

(b)

10 parts of 2-[4-(4'-trifluoromethylphenoxy)-phenoxy]-2-methoxy-aceticacid methyl ester,

3 parts of a mixture of the sodium salts of saturated fatty alcoholsulfates,

5 parts of naphthalenesulfonic acid/formaldehyde condensate,

82 parts of kaolin.

The given active substance is absorbed onto the appropriate carriers(kaolin and chalk), and the material is subsequently mixed and groundwith the remaining constituents. Wettable powders having excellentwetting and suspension properties are obtained. It is possible to obtainfrom wettable powders of this kind suspensions containing 0.1 to 80% ofactive substance, and these suspensions are suitable for combating weedsin crops of cultivated plants.

Paste

The following substances are used to produce a 45% paste:

45 parts of 2-[4-(4'-trifluoromethylphenoxy)-phenoxy]-2-methoxy-aceticacid methyl ester or of another of the stated active substances of theformula I,

5 parts of sodium aluminium silicate,

14 parts of cetyl polyglycol ether having 8 mols of ethylene oxide,

1 part of oleyl polyglycol ether having 5 mols of ethylene oxide,

2 parts of spindle oil,

10 parts of polyethylene glycol, and

23 parts of water.

The active substance is intimately mixed and ground with the additivesin apparatus suitable for the purpose. There is obtained a paste fromwhich can be produced, by dilution with water, suspensions of anydesired concentration.

Emulsion concentrate

The following constituents are mixed together to produce a 25% emulsionconcentrate:

25 parts of2-[3-(3',5'-dipyridyl-2'-oxy)-6-chlorophenoxy]-2-methoxyacetic acidmethyl ester, or of another of the stated active substances of theformula I,

5 parts of a mixture of nonylphenolpolyoxyethylene or calciumdodecylbenzene sulfate,

15 parts of cyclohexanone, and

55 parts of xylene.

This concentrate can be diluted with water to give emulsions of suitableconcentration, for example 0.1 to 10%, and emulsions of this kind aresuitable for combating weeds in crops of cultivated plants.

Compositions according to the invention which contain as activeingredient at least one compound of the formula I are suitable inparticular for selectively combating monocotyledonous wild grasses,which are difficult to control, in crops of cultivated plants, forexample wheat, and also soya-bean, cotton and sugar cane, and so forth,by pre-emergence and especially post-emergence application.

The following test methods serve to verify the suitability of the saidcompositions as herbicides (pre- and post-emergence application).

Pre-emergence herbicidal action (inhibition of germination)

Immediately after sowing the test plants in seed trays in a greenhouse,the surface of the soil is treated with an aqueous dispersion of theactive substance, which has been prepared from a 25% emulsionconcentrate, and from a 25% wettable powder containing active substanceswhich cannot be produced as emulsion concentrates owing to inadequatesolubility. Four different concentration series are used, correspondingto 4, 2, 1 and 0.5 kg of active substance per hectare. The seed traysare left in the greenhouse at 22°-25° C. with 50-70% relative humidity,and the test is evaluated after 3 weeks, with the results being assessedaccording to the following scale of ratings:

1=plants have not germinated or have fully died off,

2-3=very intense action,

4-6=moderate action,

7-8=slight action,

9=no action (as in the case of untreated control plants).

The following are used as test plants:

    ______________________________________                                        Hordeum (barley)   Setaria italica                                            Triticum (wheat)   Echinochloa crus galli                                     Zea (maize)        Beta vulgaris                                              Sorghum hybr. (millet)                                                                           Sida spinosa                                               Oryza (rice)       Sesbania exalata                                           Glycine (soya bean)                                                                              Amaranthus retroflexus                                     Gossypium (cotton) Sinapis alba                                               Avena fatua        Ipomoea purpurea                                           Lolium perenne     Galium aparine                                             Alopecurus myosuroides                                                                           Pastinaca sativa                                           Bromus tectorum    Rumex sp.                                                  Cyperus esculentus Chrysanthemum leucum                                       Rottboellia exaltata                                                                             Abutilon sp.                                               Digitaria sanguinalis                                                                            Solanium nigrum                                            ______________________________________                                    

Post-emergence herbicidal action (contact herbicide)

A largish number (at least 7) of weeds and of cultivated plants, bothmonocotyledonous and dicotyledonous, are sprayed after emergence (in the4- to 6-leaf stage) with an aqueous active-substance dispersion indosage amounts of 0.06, 0.125, 0.25, 0.5, 1, 2 and 4 kg of activesubstance per hectare, and they are then kept at 24°-26° C. with 45-60%relative humidity. The test is evaluated 15 days after treatment, andthe results are assessed according to the same scale of ratings as usedin the pre-emergence test.

Reduction of the vegetative growth of soya-bean plants

In a soya-bean field, plots each 30 by 8 foot in size are sprayed withaqueous solutions of the active substances at the point of time when thesoya plants are in the 9-10 leaf-stage. Untreated plots serve as acontrol. At the point of time of harvesting, 31/2 months after the timeof application, the mean growth in height of the plants on each plot andalso the yields are determined, and the results compared with thoseobtained on the untreated control plots.

Defoliation and desiccation in cotton crops

In a cotton field, 2 weeks before the expected point of time ofharvesting, plots each consisting of 2 rows each 20 foot long aresprayed with aqueous preparations of the active substances. Untreatedplots serve as a control. On the 3rd, 7th and 14th day afterapplication, the leaf fall and the desiccation effect on the variousplots are determined, and the results compared with those observed onthe control plots.

What is claimed is:
 1. A compound of the formula ##STR53## in which R₁is chlorine or bromine,R₂ is hydrogen, chlorine, bromine or cyano, R₃ ischlorine, bromine or nitro Z is oxygen or sulfur, and R₅ is hydrogen, C₁-C₃ alkyl, allyl, cyclohexyl, phenyl or benzyl. 2.2-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-chlorophenoxy]-2-methoxy-aceticacid methyl ester according to claim
 1. 3.2-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-bromophenoxy]-2-methoxy-aceticacid methyl ester according to claim
 1. 4.2-[3-(3',5'-Dichloropyridyl-2'-oxy)-nitrophenoxy]-2-methoxy-acetic acidmethyl ester according to claim
 1. 5. A herbicidal and plant growthregulating composition which contains as active substance an effectiveamount of a pyridyl-phenoxy-alkanecarboxylic acid derivative of claim 1,together with a suitable carrier therefor.
 6. A method for the selectivecontrol of weeds in crops of cereals or rice comprising applying theretoor to the locus thereof a herbicidally effective amount of a compoundaccording to claim 1.